Photographic process for photographic silver halide light-sensitive elements

ABSTRACT

An improved developing process for photographic silver halide elements wherein the element is subjected to processing between a prehardening step and a development step with an aqueous solution containing a heterocyclic compound having structural units which comprise at least two members which are from the group consisting of AT LEAST ONE STRUCTURAL UNIT MUST BE FROM THE GROUP CONSISTING OF R1, R2 and R3 may each be a hydrogen atom, a methyl group or an ethyl group.

United States Patent [72] Inventors l-laruhiko Iwano;

Isao Shimamura, both of Ashigarakamigun, Kanagawa, Japan [21] Appl. No. 764,591

[22] Filed Oct. 2, 1968 [45] Patented Oct. 26, 1971 [73] Assignee Fuji Shashin Film Kabushiki Kaisha [32] Priority Oct. 2, 1967 [54] PHOTOGRAPHIC PROCESS FOR PHOTOGRAPHIC SILVER HALIDE LIGHT- SENSITIVE ELEMENTS 2 Claims, No Drawings [52] US. 96/66.5, 96/50 PT, 96/ 109 [51] Int. Cl G03c 5/30, G03c 5/38 [50] Field of Search 26/665, 109, 22, 50, 50 PT [56] References Cited UNITED STATES PATENTS 1,763,989 6/1930 Sheppard et al. 96/ 109 2,184,023 12/1939 Sheppard et al. 96/109 2,319,090 5/1943 Sheppard et al. 96/109 2,354,662 8/1944 Bryce 117/156 2,697,100 12/1954 Knott 96/109 X 2,857,274 10/1958 Land et al 96/66 X 2,857,276 10/1958 Land et al 96/66 X 3,386,831 6/1968 Honig et al. 96/109 2,311,098 2/1943 Swan et a1 96/109 X Primary Examiner-William D. Martin Assistant Examiner-M. R. Lusignan AttorneySughrue, Rothwell, 'Mion, Zinn and MacPeak at least one structural unit must be from the group consisting of R,, R and R may each be a hydrogen atom, a methyl group or an ethyl group.

PHOTOGRAPI-IIC PROCESS FOR PHOTOGRAPI-IIC SILVER HALIDE LIGHT-SENSITIVE ELEMENTS BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates generally to a development process for photographic silver halide light-sensitive elements and more particularly to a process of reducing the formation of fogs caused by the hardening of silver halide emulsion layers of photographic silver halide light-sensitive elements.

2. Description of the Prior Art In general, when photographic light-sensitive films, printing papers, or photographic light-sensitive plates having silver halide are subjected to photographic processing, they are processed in a hardening bath prior to a development step.

The object of the hardening processing is to prevent the silver halide emulsion layers from being damaged mechanically or physically during the development process by increasing the mechanical or physical strength of the emulsion layers. In particular, the application of the hardening bath is very effective when silver halide emulsion layers do not originally have sufficient strength, the emulsion layers are to be processed for a long period of time, or the emulsion layers are to be processed in a solution having either a high temperature or a high pH. The hardening processing used prior to development is usually called prehardening, and as a prehardening bath, there is usually employed an aqueous solution containing an aldehyde capable of hardening the gelatin in the photographic emulsion layer by the reaction therewith, such as, formaldehyde, glyoxal, succinealdehyde, glutaraldehyde, etc.

Although the use of such a prehardening bath effectively hardens photographic emulsion layers, it gives a bad influence on photographic properties, for example, the formation of development fogs is increased, the development density at reversal development is reduced, and the coupling property of couplers in photographic light-sensitive color elements is varied.

SUMMARY OF THE INVENTION It has been found that the formation of fogs caused by the hardening of silver halide emulsion layers in photographic light-sensitive elements may be reduced in a processing scheme wherein a prehardening step and a development step is utilized by subjecting the element to a processing step between prehardening and development which comprises subjecting the element to an aqueous solution containing a heterocyclic compound having structural units which comprise at least two members which are from the group consisting of At least one of the structural units must be from the group consisting of II I I- and R,, R, and R are selected from the group consisting of a hydrogen atom, a methyl group and an ethyl group.

The heterocyclic compound is generally utilized in a concentration ofO. 1-50 g./liter.

Thus, an object of the present invention is to provide an improved method of processing photographic silver halide lightsensitive elements which provides good photographic properties and sufficient mechanical strength to photographic emulsion layers, without any of the faults known in the prior art.

DESCRIPTION OF THE PREFERRED EMBODIMENTS According to the process of the present invention, photographic silver halide emulsion layers are processed between prehardening processing and development processing in an aqueous solution containing a heterocyclic compound (including a tautomer thereof) having as structural units at least two of the groups:

H 0 R1 R2 l g l l -N, C: and (IJ (at least one of which H r -N or C wherein R R and R may represent a hydrogen atom, a methyl group or an ethyl group.

Typical examples of such compounds are maleic hydrazide, dimedone, uracil, cyanuric acid, succinimide, flavanic acid, barbituric acid, and melamine.

By using the aforesaid heterocyclic compound, generally in a concentration of 0.! -50 g./liter, the aldehyde remaining after hardening processing is effectively removed, whereby the entrance of the aldehyde in the subsequent processing step is effectively prevented.

The aqueous solution for antifogging processing is preferred and may be used at any pH, but better results can be obtained when it is used in a neutral or acid state. Moreover, the aqueous solution containing the aforesaid heterocyclic compound may further contain pH-controlling agents and buffering agents, such as sodium sulfate, borax, acetic acid, sodium acetate, sodium carbonate, sulfuric acid, boric acid, etc., and also other general antifogging agents, such as an alkali halide.

The light-sensitive emulsion layer to be processed by the process of this invention contains, as a light-sensitive material, a conventionally-employed silver halide, and as a dispersoid for the light-sensitive material, gelatin or a mixture of gelatin and another hydrophilic high molecular weight material. Supports for the photographic emulsion layers may be glass plates, cellulose ester films, polyester films, and papers. These are commonly used in the photographic art.

The process of this invention may most suitably be applied to the case of processing light-sensitive reversal color elements which are processed at a high pH or for a long period of time; it is also particularly applicable to color photographic printing papers which are preferably quickly processed at high temperature.

In the practice of the process of this invention, a photographic light-sensitive element is, after being subjected to prehardening processing, processed in the antifogging bath of this invention, and thereafter subjected to conventional subsequent processings, including development.

By the process of the present invention, the formation of development fogs is lessened, reduction in development density does not occur, and the coupling property of couplers in light-sensitive color elements is not varied.

The following examples will further explain the process of this invention in detail, although the invention is not limited to them.

EXAMPLE l A black and white negative photographic light-sensitive film prepared by applying a gelatino silveriodobromide emulsion sufficiently panchromatically color sensitized was exposed by means of a sensitometer and subjected to the following photographic processings at 40 C.:

Processing Time Prehardening 35 sec. Washing 10 sec. Antifogging processing 45 sec. Washing 20 sec. Development 50 sec.

The compositions of the processing solutions used in the Stopping Fixing Washing above processings are as follows:

Prehardening composition:

Sodium bisulfite Fonnalin (37% aq. soln.) Borax Sodium sulfate Potassium bromide Water to make Antifogging composition:

The heterocyclic compound shown in the following table was dissolved in 1 liter of an aqueous solution containing 5 g. of glacial acetic acid and 4 g. of sodium acetate to provide seven different embodiments of the antifogging baths of this invention. A control solution which did not contain the l sec.

30 see.

90 sec.

heterocyclic compound of this invention was also prepared.

The results of the photographic processings are shown in table I, in which the relative sensitivity is shown by the logarithmic value of a reciprocal of the exposure amount cor- Water to make I 'er responding to the blackened density ofa 0.1 over fog.

TABLE 1 cal strength of the photographic emulsion layer is increased, and hence high-temperature processing can be applied without being accompanied by operational problems.

EXAMPLE 2 A photographic gelatino silver halide emulsion layer (panchromatically color-sensitized and applied to a polyester film) was exposed through a silver step wedge by means of a sensitometer and subjected to the following photographic l0 processings at 27 C.:

Process Time 5 Prehardening 60 sec. Washing 30 sec. Antifogging processing 60 sec. Washing 30 sec. Primary development 2 l0 sec Washing 30 sec.

Bleaching I80 sec Washing 30 sec. Cleaning 60 sec. Washing 30 SEC. Second development 120 sec Washing sec. 30 Fixing 90 sec.

Washing 150 sec Drying I80 sec.

ln the above processings, only drying was conducted at 38 C. The compositions of the processing solutions used in the above processings are as follows:

Prehardening composition: Same as in example I. Antifogging composition Theheterocyclic compound shown in the following table was added to 1 liter of an aqueous solution containing 4 g. of

sodium acetate, 5 ml. of glacial acetic acid, and 0.7 g. of potassium bromide.

Test No. Additive Amount 1 none 2 maleic hydrazide 2 g.

3 dimedone 2 g. 4 uracil 3 g.

S cyanuric acid 5 g.

Primary and secondary developers:

0.8 g./liter of potassium thiocyanate was added to the developer in example 1.

Bleaching solution:

Sulfuric acid 5 ml.

Potassium bichromate g.

Water to make 1 liter Test No. Fog Relative Sensitivity Gamma va|uc Cleaning composition:

Sodium sullite 50 g. Water to make l liter I (control) 0.36 2.20 0.32 2 0.23 2.3 5 0.37 Fixing composition: 3 0.25 2.33 0.36 Same as in example 1. 4 0.22 2.36 0.36 s 0.24 2.33 tm 0.35 6 M5 5 M5 The results are shown In table 2. 1 0.25 2.32 0.35 a 0.24 2.34 0.36 TABLE 2 No bath (control) 0.37 2.20 0.31

PS Test No Reversal density It IS clear from the results shown in the above table that by the application of the antifogging bath of this invention, the l (COMM, H2 formation of development fogs was effectively prevented and 2 1.52 the sensitivity and the gamma value were increased. 3 In addition, the application of the antifogging bath enables 5 f:

the practice of prehardening processing whereby the mechani- Reversal exposure (blue light) 200 CMS from the emulsion layer side of the film.

ty) thus obtained are shown in the following table.

Z-Amino-S-diethylaminotoluene sulfate 0.6 g. It is clear from the above results that since the reversal denigf 'l'z' rfi g'x j '3; sity was increased by the use of the antifogging bath of this inpomium iodide (on W. mm vention, good photographic properties were obtained while l,5-Dihydroxy-2.6-dibromonaphthalene 1.2 I employing the prehardening processing. Furthermore, by the a' hydmid' 8 process of this invention the surface of the photographic emul- Yen 7: 2:32:; I sion layer was prevented from being damaged mechanically sodium 50 l during processing and the drying load for the photographic N.N-Dilhyl-p-pehnylenediaminesulfite 2.5 g. film was reduced. f P' It Potassium iodide (01% aq. soln.) 5.0 ml. EXAMPLE, 3 u-Benzoyl-4-p-(toluenesulfonamide)- acetanilide 1.2 g s a h d a A multiple layer photographic color film prepared by apply- 5 3: c ing to a cellulose acetate film a gelatino silver iodobromide emulsion having a red sensitivity, a gelatino silver iodobrol 5 Magma colmdevelopfl: mide emulsion having a green sensitivity, a yellow filter layer Sodium sulfite 5.0 g containing fine colloidal silver particles andhave a blue-ab- Z-Aminv-fiifthylaminvwluene sorptive property, and a gelatino silver iodobromide emulsion 'gs zfrr 'js 3 having a blue sensitivity (in this order) and exposed through a l pheny| 3 (mmilmbmwlamim), silver step wedge by means of a sensitometer was subjected to S-pyrazolone L4 8 the following processings at 24 C.: *X 8- n-Butylamine 5.0 3. Water to make I liter Processing Time P h a l z fi I Bleaching solution: Amirouinl pmcemng I min 25 Potass um ferricyanide 100 t g. washing I min Potassium bromide 20 g. Primary development 5 min. washing 2 min. Boric acid 1.0 Water to make I liter Reversal exposure (red light) 200CMS from the back side of the film Fixing solution:

' Sodium thiosulfaie I50 g. Sodium sull'ite l0 g. Cyan color development 5 min. make Washing 2min.

The photographic characteristics (reversal coupling densi- Yellow color development 5 min. 3 Washing l min. Secondary development l min. 4() Washing l Test No. Reversal density Red density Green density Blue density Reversal exposure (white light) 2000 CMS from the opposite sides of the film. I 305 2.95 no 2 3.43 3.40 3.44

Magenta color developer 5 min. 3 3.47 3.42 3.46 Washi 5 i 4 3.48 3.38 3.47 Bleaching 2 min. 5 0 3.42 Washing l min. 6 3.44 3.42 3.42 Fixing 2 min. 7 4 3.40 3.40 Washing 2 min. 5 8 3.43 3.4l 3.4]

The compositions for the above processings are as follows:

Prehardening composition:

Same as in example 1.

Antifogging composition: 5 5

The heterocyclic compound shown in the following table was added to lliter of an aqueous solution containing 8 g. of boric acid, 0.3 ml. of sulfuric acid and 0.8 g. of potassium bro- From the results, it is confirmed that the coupling densities were remarkably increased by the antifogging processing of this invention. Furthermore, contamination. decrease in sensitivity and other harmful influences on the photographic properties of the film were not observed.

mid?" EXAMPLE 4 A commercially available color photographic printing paper was exposed by means of a sensitometer and then processed as T i v Amount follows at 20 C. (except drying, which was conducted at 38 I (control) none 2 maleic hydrazide 2 g. Processing l Time 3 dimedone 2 g. Color development 5 min. 4 uracil 3 g. Washing 5 min. 5 cyanuric acid 5 g. Bleach-fixing 8 min. 6 succlnirnide 5 g. Washing l0 min. 7 flavanic acid 5 g. Hardening 5 min. 8 barbituric acid 2 g. Buffering processing 5 min. Washing 5 min. Stabilization 5 min. Drying 5 min. Primary and secondary black and white developer:

Same as in Example 2. g Cyan color develop": The compositions used in the above processings are as fol- Sodium time 5.0 g. lows:

Color developer:

N -ethyl-n-hydroxyethyl-p-phenylene- Sodium bisull'ite 4 g. Water to make I liter Buffering composition:

Tartaric acid l g. Borax 25 g. Water to make 1 er Stabilization Composition:

Whitening agent (Tinopol: trade name.

made by Geigy A.G.) 4 g. Sodium dihydrogen phosphate 4 g. Disodium hydrogen phosphate 2 g. Tetrasodium suit of ethylenediaminetetraaectic acid I g Water to make I er Although good photographic qualities were obtained by the above processing, there was one fault and that was that exposed printing paper had to be processed for a longer period of time. Thus, to reduce the processing time, the whole processing was conducted at 35 C. (processing ll.) However, a so-called reticulation was formed on the emulsion layer, and this reduced the commercial value of the printing paper.

To obviate this, the hardening step was carried out prior to the color development step (processing Ill.) That is, the hardening process in processing l was omitted, and as a substitute therefore the printing paper was processed for 60 seconds before the color development in a hardening solution having the following composition:

Hardening composition:

Formalinfl'lZ aq.soln.) 20 ml. 2.S-dimethoxytetrahydrol'urun 4 ml. Sulfuric acid 2 ml. Sodium sulfate I00 g. Potassium bromide 2 g. Borax 5 g Water to make er By this processing, the mechanical strength of the light-sensitive emulsion layer of the printing paper was sufficiently increased, but development fogs were severely formed by processing III. This also reduced the commercial value of the printing paper, the same as in processing ll.

However, when the printing paper was subjected to the processings of this invention (after exposure) employing antil'ogging processing (processing lV,) good photographic qualities as in the standard processing (processing l) were obtained, and the processing time was shortened as shown below while maintaining sufficient mechanical strength of the photographic emulsion layer of the printing paper during processing. The following processings were conducted at 38 C. (except drying, which was conducted at 50 C.)

Processing lV Time Hardening 60 sec. Washing 30 sec. Antifogglng processing 60 sec.

washing 30 sec. Color development I00 sec. Washing 30 sec. Bleach-fixing I40 sec. Washing 30 sec. Buffering processing 40 sec. Washing 30 sec. Stabilization 40 sec. Drying The composition for the antifogging processing was an aqueous solution containing 3 g./liter of uracil and 0.5 g./liter of potassium bromide. The composition for the hardening processing was the same as in processing ill.

The fogging densities of the color printing papers obtained by processings I, II, III, and IV are shown in the following table.

TABLE 4 Processing Fog Density Red density Green density Blue density 0.08 0.08 0.l I II O.l0 0.09 0. l l

EXAM PLE 5 A gelatino silver halide emulsion layer having a red sensitivity formed on a cellulose acetate film was exposed by means of a sensitometer through a silver step wedge and then subjected to the following reversal color processing at 24 C.:

Processing: Time Prehardening 60 sec. Washing 60 sec. Antifogging processing 60 sec. Washing 60 sec. Primary development 2 l0 sec. Washing 60 sec.

Reversal exposure at 200 CMS. under white light.

Cyan development 210 sec. Washing 60 sec. Bleaching 60 sec. Washing (i0 sec. Fixing 60 sec. Washing 60 sec.

The compositions for the prehardening and antifogging processings used above were the same as in example i, the other compositions being the same as in example 3. The results are shown in the following table.

By using the antifogging bath, the coupling density was remarkably increased, as shown in the above table.

EXAMPLE 6 Reversal magnenta color development was conducted basically as in example 5. Specifically, the cyan color developer in Example 5 was replaced with the magenta color developer in example 3, and as the antifogging composition, the following solution was employed. However, the same basic procedure as in example was repeated. The composition for the antifogging processing used in this example was an aqueous solution containing 50 g./liter of sodium sulfate, 5.0 g./liter of 5 sodium bisulfite, 1.0 g./liter of borax, 0.5 g./liter of potassium bromide, and the heterocyclic compound shown in the following table.

Telt No. Additive Amount (gJliter) l none 2 Dirncdone 4 3 Uracil 3 4 Cyanuric acid 5 5 Barbituric acid 2 The results are shown in the following table.

TABLE 6 Tell No. Reversal density I (control) 2 3 2.29 4

What is claimed is: 1. In a photographic processing method comprising preat least one of said structural units being a member selected from the group consisting of:

wherein R lfpand g each reprcsents a member selected from the group consisting of a hydrogen atom, a methyl group, and an ethyl group.

2. The photographic processing method as claimed in claim 1 wherein said heterocyclic compound is selected from the group consisting of hydrazide, dimedone, uracil. cyanuric acid, succinimide flavanic acid, barbituric acid, and melamine. 

2. The photographic processing method as claimed in claim 1 wherein said heterocyclic compound is selected from the group consisting of hydrazide, dimedone, uracil, cyanuric acid, succinimide, flavanic acid, barbituric acid, and melamine. 